CN112094616A - High-thixotropy and fast-curing single-component low-modulus polyurethane sealant and preparation method thereof - Google Patents
High-thixotropy and fast-curing single-component low-modulus polyurethane sealant and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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Abstract
The invention provides a high-thixotropy fast-curing single-component low-modulus polyurethane sealant and a preparation method thereof, wherein the preparation raw materials comprise the following components: 25-45 parts of polyurethane prepolymer, 0-20 parts of plasticizer a, 30-50 parts of filler, 15-35 parts of thixotropic agent, 0.2-2 parts of water absorbent, 1-4 parts of synthetic coupling agent and 0.01-1 part of catalyst a; the synthetic coupling agent is prepared by reacting isocyanate b and silane; the silane is selected from secondary aminosilane and/or mercaptosilane; the thixotropic agent is prepared by reacting monoamine compounds with isocyanate a in the presence of a plasticizer b. The polyurethane sealant adopts a synthetic coupling agent, and can achieve primer-free bonding of building concrete under the combined action of a polyurethane prepolymer; the thixotropic agent has better thixotropic property on the premise of not increasing the strength, and can also meet the low modulus characteristic of the polyurethane sealant. And also has a faster curing speed.
Description
Technical Field
The invention belongs to the technical field of polyurethane, and particularly relates to a high-thixotropy fast-curing single-component low-modulus polyurethane sealant and a preparation method thereof.
Background
The single-component polyurethane sealant is a polyurethane adhesive which takes a polymer blocked by an isocyanate (NCO) group as a main effective component and is matched with a plasticizer, a filler, a catalyst and an auxiliary agent.
Patent application No. 200510102933.2 discloses a direct-bonding polyurethane sealant, wherein the coupling agent is commercial silane coupling agent, and the curing strength of polyurethane adhesive can be affected by the direct addition of the coupling agent. The CN111073588A primer-free single-component polyurethane adhesive sealant and the preparation method thereof and the CN111378413A primer-free single-component polyurethane sealant and the preparation method thereof all adopt similar schemes, and the curing speed of the product is relatively slow.
Therefore, the curing speed of the single-component low-modulus polyurethane sealant on the market is slow, and the defect that the requirement of quick operation cannot be met exists.
Disclosure of Invention
In view of the above, the invention aims to provide a high-thixotropy and fast-curing single-component low-modulus polyurethane sealant and a preparation method thereof.
The invention provides a high-thixotropy fast-curing single-component low-modulus polyurethane sealant, which comprises the following raw materials in parts by weight:
25-45 parts of polyurethane prepolymer, 0-20 parts of plasticizer a, 30-50 parts of filler, 15-35 parts of thixotropic agent, 0.2-2 parts of water absorbent, 1-4 parts of synthetic coupling agent and 0.01-1 part of catalyst a;
the synthetic coupling agent is prepared by reacting isocyanate b and silane; the silane is selected from secondary aminosilane and/or mercaptosilane;
the thixotropic agent is prepared by reacting monoamine compounds with isocyanate a in the presence of a plasticizer b.
Preferably, the secondary aminosilane is selected from one or more of bis- (gamma-trimethoxysilylpropyl) amine, N-phenyl-gamma-aminopropyltrimethoxysilane, N-phenyl-gamma-aminopropyltriethoxysilane, N-butyl-gamma-aminopropyltrimethoxysilane, N-butyl-gamma-aminopropyltriethoxysilane, N-ethyl-3-aminopropyltrimethoxysilane and N-ethyl-3-aminopropyltriethoxysilane;
the mercaptosilane is selected from gamma-mercaptopropyltrimethoxysilane and/or gamma-mercaptopropyltriethoxysilane.
Preferably, the isocyanate b is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate trimer, isophorone diisocyanate trimer, and hexamethylene diisocyanate trimer.
Preferably, the molar ratio of the isocyanate b to the silane is 1: 0.8-2.0;
the reaction temperature is 50-70 ℃, and the reaction time is 1-4 h.
Preferably, the plasticizer a is selected from one or more of alkyl sulfonate, phthalate, cyclohexane dicarboxylate, phosphate triester and citrate triester;
the filler is selected from one or more of ground silica, ground calcium carbonate, talcum powder, clay, organic bentonite, hydrogenated castor oil and barium sulfate;
the water absorbent is selected from one or more of alkyl sulfonic acid isocyanate, calcium oxide and molecular sieve;
the catalyst a is selected from tertiary amine catalysts and/or tin catalysts.
Preferably, the monoamine compound is selected from one or more of methylamine, ethylamine, n-propylamine, n-butylamine, pentylamine, n-hexylamine, n-octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, aniline, methylaniline, ethylaniline, diphenylamine, dimethylaniline and diethylaniline;
the isocyanate a is selected from toluene diisocyanate, diphenylmethane diisocyanate, 1, 4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, tolidine diisocyanate, 1, 5-naphthalene diisocyanate, triphenylmethane triisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, trans-cyclohexane-1, 4-diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, TDI trimer, IPDI trimer, HDI trimer, polymeric MDI, biuret group-modified MDI, isocyanurate group-modified MDI, urethane group-modified MDI, MDI, One or more of uretdione group-modified MDI, carbodiimide group-modified MDI, and allophanate group-modified MDI;
the plasticizer b is one or more selected from alkyl sulfonate, phthalate, cyclohexane dicarboxylate, phosphate triester and citrate triester.
Preferably, the polyurethane prepolymer is prepared by reacting polyether polyol and isocyanate c in the presence of a catalyst b;
the polyether polyol is selected from polyether triol with the molecular weight of 3000-6000 and/or polyether diol with the molecular weight of 1000-4000;
the isocyanate c is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, 1, 4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, tolidine diisocyanate, 1, 5-naphthalene diisocyanate, triphenylmethane triisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, trans cyclohexane-1, 4-diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane and dicyclohexylmethane diisocyanate;
the catalyst b is selected from one or more of dioctyltin dilaurate, dibutyltin dilaurate, dimethyltin dilaurate, stannous octoate, butyltin oxide and octyltin oxide.
The invention provides a preparation method of a single-component low-modulus polyurethane sealant, which comprises the following steps:
and uniformly mixing the polyurethane prepolymer, the plasticizer, the filler, the water absorbent and the thixotropic agent under a vacuum condition, adding the synthetic coupling agent and the catalyst a, and uniformly stirring to obtain the high-thixotropy and fast-curing single-component low-modulus polyurethane sealant.
The invention provides a high-thixotropy fast-curing single-component low-modulus polyurethane sealant, which comprises the following raw materials in parts by weight: 25-45 parts of polyurethane prepolymer, 0-20 parts of plasticizer a, 30-50 parts of filler, 15-35 parts of thixotropic agent, 0.2-2 parts of water absorbent, 1-4 parts of synthetic coupling agent and 0.01-1 part of catalyst a; the synthetic coupling agent is prepared by reacting isocyanate b and silane; the silane is selected from secondary aminosilane and/or mercaptosilane; the thixotropic agent is prepared by reacting monoamine compounds with isocyanate a in the presence of a plasticizer b. The polyurethane sealant adopts a synthetic coupling agent, and can achieve primer-free bonding of building concrete under the combined action of a polyurethane prepolymer; the thixotropic agent has better thixotropic property on the premise of not increasing the strength, and can also meet the low modulus characteristic of the polyurethane sealant. And also has a faster curing speed. The experimental results show that: the curing speed of the single-component low-modulus polyurethane sealant is 4-4.4 mm/24h (23 ℃, 50% RH); the 100% tensile strength is 0.29-0.37 MPa; the tensile strength is 1.7-1.94 MPa; concrete adhesion: cohesive failure rate of 100%; the storage change rate (54 ℃, 3d) is 22 to 33 percent; the thixotropy is good.
Detailed Description
The invention provides a high-thixotropy fast-curing single-component low-modulus polyurethane sealant, which comprises the following raw materials in parts by weight:
25-45 parts of polyurethane prepolymer, 0-20 parts of plasticizer a, 30-50 parts of filler, 15-35 parts of thixotropic agent, 0.2-2 parts of water absorbent, 1-4 parts of synthetic coupling agent and 0.01-1 part of catalyst a;
the synthetic coupling agent is prepared by reacting isocyanate b and silane; the silane is selected from secondary aminosilane and/or mercaptosilane;
the thixotropic agent is prepared by reacting monoamine compounds with isocyanate a in the presence of a plasticizer b.
The single-component low-modulus polyurethane sealant provided by the invention comprises 25-45 parts of polyurethane prepolymer. In specific embodiments of the invention, the polyurethane prepolymer is used in an amount of 25 parts, 35 parts, or 45 parts. The polyurethane prepolymer is prepared by reacting polyether polyol with isocyanate c in the presence of a catalyst b; the mass ratio of the polyether polyol to the isocyanate c to the catalyst b is 100: 5-20: 0.01-0.05. The polyether polyol is preferably selected from polyether triol with the molecular weight of 3000-6000 and/or polyether diol with the molecular weight of 1000-4000. The isocyanate c is preferably selected from the group consisting of Tolylene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1, 4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, Xylylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1, 5-Naphthalene Diisocyanate (NDI), one or more of triphenylmethane triisocyanate, Hexamethylene Diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), trans-cyclohexane-1, 4-diisocyanate, isophorone diisocyanate (IPDI), bis (isocyanatomethyl) cyclohexane (H6XDI), and dicyclohexylmethane diisocyanate (H12 MDI); more preferably selected from diphenylmethane diisocyanate; the diphenylmethane diisocyanate is selected from 4,4 '-MDI and/or 2, 4' -MDI. In a particular embodiment, the isocyanate c is preferably selected from 4, 4' -MDI. The catalyst b is preferably selected from one or more of dioctyltin dilaurate, dibutyltin dilaurate, dimethyltin dilaurate, stannous octoate, butyltin oxide and octyltin oxide.
The mass content of NCO in the polyurethane prepolymer is 2.20-2.61%; in particular embodiments, the NCO mass content is 2.20%, 2.23%, or 2.61%.
The single-component low-modulus polyurethane sealant provided by the invention comprises 0-20 parts of plasticizer a. In specific embodiments, the plasticizer a is used in an amount of 0 part, 10 parts, or 20 parts. The types of the plasticizer a and the plasticizer b are the same, and when specifically selected, the plasticizers may be the same or different. The plasticizer a and the plasticizer b are independently selected from one or more of alkyl sulfonate, phthalate, cyclohexane dicarboxylate, phosphoric acid triester and citric acid triester, and are more preferably selected from phthalate and/or cyclohexane dicarboxylate; in particular embodiments, the plasticizer is a phthalate; the phthalate is diisononyl phthalate (DINP) and/or diisodecyl phthalate (DIDP).
The single-component low-modulus polyurethane sealant provided by the invention comprises 30-50 parts of filler. In particular embodiments, the filler is used in an amount of 50 parts, 40 parts, or 30 parts. The filler is preferably selected from one or more of ground silica, ground calcium carbonate, talc, clay, organobentonite, hydrogenated castor oil and barium sulphate; more preferably from ground calcium carbonate.
The single-component low-modulus polyurethane sealant provided by the invention comprises 15-35 parts of thixotropic agent. In particular embodiments, the thixotropic agent is used in an amount of 15 parts, 25 parts, or 35 parts. The thixotropic agent is prepared by reacting monoamine compounds with isocyanate a in the presence of a plasticizer b. The molar ratio of the monoamine compound to the isocyanate a is 1: 1.05-1.0; the mass content of the plasticizer b in the thixotropic agent is 50-80%.
The monoamine compound is preferably selected from one or more of methylamine, ethylamine, n-propylamine, n-butylamine, pentylamine, n-hexylamine, n-octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, aniline, methylaniline, ethylaniline, diphenylamine, dimethylaniline and diethylaniline; more preferably selected from di-n-butylamine.
The isocyanate a is selected from toluene diisocyanate, diphenylmethane diisocyanate, 1, 4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, tolidine diisocyanate, 1, 5-naphthalene diisocyanate, triphenylmethane triisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, trans-cyclohexane-1, 4-diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, TDI, IPDI trimer, HDI trimer, polymeric MDI, biuret group-modified MDI, isocyanurate group-modified MDI, urethane group-modified MDI, MDI, One or more of uretdione group-modified MDI, carbodiimide group-modified MDI, and allophanate group-modified MDI; more preferably selected from diphenylmethane diisocyanates (MDI).
The single-component low-modulus polyurethane sealant provided by the invention comprises 0.2-2 parts of water absorbent. In specific examples, the water absorbing agent is used in an amount of 0.2 parts, 2 parts, 0.5 parts, or 1 part. The water absorbent is preferably selected from one or more of alkyl sulfonic acid isocyanate, calcium oxide and molecular sieve; more preferably from calcium oxide.
The single-component low-modulus polyurethane sealant provided by the invention comprises 1-4 parts of synthetic coupling agent. In specific examples, the synthetic coupling agent is used in an amount of 1 part, 2 parts, or 4 parts. The synthetic coupling agent is prepared by reacting isocyanate b and silane; the silane is selected from secondary aminosilane and/or mercaptosilane; the secondary aminosilane is selected from one or more of bis- (gamma-trimethoxysilylpropyl) amine, N-phenyl-gamma-aminopropyltrimethoxysilane, N-phenyl-gamma-aminopropyltriethoxysilane, N-butyl-gamma-aminopropyltrimethoxysilane, N-butyl-gamma-aminopropyltriethoxysilane, N-ethyl-3-aminopropyltrimethoxysilane and N-ethyl-3-aminopropyltriethoxysilane; the mercaptosilane is selected from gamma-mercaptopropyltrimethoxysilane and/or gamma-mercaptopropyltriethoxysilane. The isocyanate b is preferably selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate trimer, isophorone diisocyanate trimer and hexamethylene diisocyanate trimer, and more preferably from one or more of TDI trimer, IPDI trimer and HDI trimer. In a specific embodiment, the isocyanate b is an HDI trimer and/or a TDI trimer; the silane is selected from N-phenyl-gamma-aminopropyltrimethoxysilane and/or gamma-mercaptopropyltrimethoxysilane.
In the present invention, the molar ratio of the isocyanate b to the silane is preferably 1:0.8 to 2.0, and more preferably 1:1.0 to 2.0. The reaction temperature is preferably 50-70 ℃, and the reaction time is 1-4 h. In specific embodiments, the temperature of the reaction is 50 ℃ or 70 ℃; the time is 1h or 4 h.
The single-component low-modulus polyurethane sealant provided by the invention comprises 0.01-1 part of catalyst a; the catalyst a is selected from tertiary amine catalysts and/or tin catalysts. In specific embodiments, the catalyst a is used in an amount of 0.2 parts, 0.3 parts, or 0.5 parts. The catalyst a is dimorpholinodiethyl ether (DMDEE) and/or dibutyltin dilaurate (DBTDL).
The invention provides a preparation method of a single-component low-modulus polyurethane sealant, which comprises the following steps:
and uniformly mixing the polyurethane prepolymer, the plasticizer, the filler, the water absorbent and the thixotropic agent under a vacuum condition, adding the synthetic coupling agent and the catalyst a, and uniformly stirring to obtain the high-thixotropy and fast-curing single-component low-modulus polyurethane sealant.
In the present invention, the polyurethane prepolymer is preferably prepared according to the following method:
the polyether polyol, the isocyanate a and the catalyst b are reacted according to the mass ratio of 100: 5-20: 0.01-0.05 to obtain the polyurethane material.
The polyether polyol is preferably heated to 110-130 ℃ for dehydration for 2h, then cooled to 50 ℃, added with isocyanate a and a catalyst b, heated to 75-90 ℃, stirred for reaction for 2-6 h, and cooled to below 50 ℃ after the-NCO content reaches a set value, so as to obtain the polyurethane prepolymer.
The plasticizer a and the plasticizer b are preferably dehydrated for 2 hours in vacuum at the temperature of 110-130 ℃ for standby;
the filler and the nano calcium carbonate are preferably dried in vacuum at 120 ℃ for 24 hours until the water content is 1500ppm for later use.
The thixotropic agent is prepared by reacting monoamine compounds with isocyanate a in the presence of a plasticizer b. Preferably, the thixotropic agent is prepared according to the following method:
dissolving the monoamine compound into part of the plasticizer b to obtain a solution containing the monoamine compound;
adding isocyanate a into the rest of plasticizer b to obtain a solution containing isocyanate a;
dropwise adding a solution containing a monoamine compound into a solution containing isocyanate a, and reacting to obtain a paste;
and grinding the paste to obtain the thixotropic agent.
In the present invention, the mass ratio of the solution containing the monoamine compound to the solution containing the isocyanate a is preferably 1: 0.95 to 1.05, and more preferably 1:1.
In the invention, the vacuum degree adopted under the vacuum condition is not lower than 980 mbar.
The invention adopts the method in HG/T4363-.
The method adopts the method in HG/T4363-; the modulus at 100% definite elongation is less than 0.4MPa, which is the low modulus.
The thixotropy is tested by adopting the method in HG/T4363-.
The invention adopts the method in JC/T482-2003 to test the adhesion of concrete.
To further illustrate the present invention, the highly thixotropic, fast curing one-component, low modulus polyurethane sealant and method of making the same provided by the present invention will now be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Preparatory example 1
Heating 1000g of polyether triol (average molecular weight 5000) and 500g of polyether diol (average molecular weight 2000) to 130 ℃ for dehydration for 2 hours, then cooling to 50 ℃, adding 258g of 4,4 '-diisocyanatophenylmethane (4, 4' -MDI) (NCO/OH is 1.8) and 0.15g of dibutyltin dilaurate, mixing, heating to 90 ℃ and reacting for 3 hours to obtain a polyurethane prepolymer A1 with the NCO% content of 2.20%;
heating 1000g of polyether triol (average molecular weight 5000) and 500g of polyether diol (average molecular weight 2000) to 130 ℃ for dehydration for 2 hours, then cooling to 50 ℃, adding 275g of 4,4 '-diisocyanate phenyl methane (4, 4' -MDI) (NCO/OH is 2.0) and 0.45g of butyl tin oxide, mixing, heating to 75 ℃ for reaction for 5 hours, and obtaining a polyurethane prepolymer A2 with the NCO% content of 2.64%;
heating 1500g of polyether triol (average molecular weight 6000) to 130 ℃ for dehydration for 2 hours, then cooling to 50 ℃, adding 210g of 4,4 '-diisocyanate phenyl methane (4, 4' -MDI) (NCO/OH is 2.2) and 0.82g of dioctyltin dilaurate, mixing, heating to 80 ℃ and reacting for 4 hours to obtain the polyurethane prepolymer A3 with the NCO% content of 2.23%.
And reacting the TDI tripolymer with N-phenyl-gamma-aminopropyltrimethoxysilane at the molar ratio of 1:1.0 at 50 ℃ for 1h to obtain the synthetic coupling agent B1.
HDI tripolymer and gamma-mercaptopropyltrimethoxysilane are reacted for 4 hours at 70 ℃ according to the molar ratio of 1:2.0 to obtain the synthetic coupling agent B2.
129.2g of di-n-butylamine (DNBA) was added to 370.8g of dehydrated DIDP, and dissolved by stirring; adding 125.1g of diphenylmethane diisocyanate (MDI) into 374.9g of dehydrated DIDP, and stirring for dissolving; slowly dripping the DNBA solution into the MDI solution under stirring to react to form white paste; grinding the white paste on a three-roll grinder to obtain the thixotropic agent.
Examples 1 to 6
Adding the polyurethane prepolymer, the dehydrated plasticizer, the water absorbent, the dried filler and the thixotropic agent in preparation example 1 into a planetary mixer according to the dosage in tables 1 and 2, uniformly mixing under vacuum condition with the vacuum degree of not less than 980mbar, then adding the synthetic coupling agent and the catalyst a, and uniformly stirring to obtain the high-thixotropy and fast-curing single-component low-modulus polyurethane sealant.
Comparative examples 1 to 2
Adding the polyurethane prepolymer A1 in the preparation example 1, the dehydrated plasticizer, the water absorbent, the dried filler and the nano calcium carbonate into a planetary mixer according to the dosage in the table 2, uniformly mixing under the vacuum condition, wherein the vacuum degree is not less than 980mbar, then adding the coupling agent gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and the catalyst a, and uniformly stirring to obtain the single-component polyurethane sealant.
TABLE 1 Performance test results for polyurethane sealants prepared in examples 1-4
TABLE 2 Performance test results of the polyurethane sealants prepared in examples 5 to 6 and comparative examples 1 to 2
The embodiment shows that the invention provides a high-thixotropy and fast-curing single-component low-modulus polyurethane sealant, which comprises the following raw materials in parts by weight: 25-45 parts of polyurethane prepolymer, 0-20 parts of plasticizer a, 30-50 parts of filler, 15-35 parts of thixotropic agent, 0.2-2 parts of water absorbent, 1-4 parts of synthetic coupling agent and 0.01-1 part of catalyst a; the synthetic coupling agent is prepared by reacting isocyanate b and silane; the silane is selected from secondary aminosilane and/or mercaptosilane; the thixotropic agent is prepared by reacting monoamine compounds with isocyanate a in the presence of a plasticizer b. The polyurethane sealant adopts a synthetic coupling agent, and can achieve primer-free bonding of building concrete under the combined action of a polyurethane prepolymer; the thixotropic agent has better thixotropic property on the premise of not increasing the strength, and can also meet the low modulus characteristic of the polyurethane sealant. And also has a faster curing speed. The experimental results show that: the curing speed of the single-component low-modulus polyurethane sealant is 4-4.4 mm/24h (23 ℃, 50% RH); the 100% tensile strength is 0.29-0.37 MPa; the tensile strength is 1.7-1.94 MPa; concrete adhesion: cohesive failure rate of 100%; the storage change rate (54 ℃, 3d) is 22 to 33 percent; the thixotropy is good.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A high-thixotropy fast-curing single-component low-modulus polyurethane sealant comprises the following preparation raw materials in parts by weight:
25-45 parts of polyurethane prepolymer, 0-20 parts of plasticizer a, 30-50 parts of filler, 15-35 parts of thixotropic agent, 0.2-2 parts of water absorbent, 1-4 parts of synthetic coupling agent and 0.01-1 part of catalyst a;
the synthetic coupling agent is prepared by reacting isocyanate b and silane; the silane is selected from secondary aminosilane and/or mercaptosilane;
the thixotropic agent is prepared by reacting monoamine compounds with isocyanate a in the presence of a plasticizer b.
2. The one-component low-modulus polyurethane sealant according to claim 1, wherein said secondary aminosilane is selected from one or more of bis- (gamma-trimethoxysilylpropyl) amine, N-phenyl-gamma-aminopropyltrimethoxysilane, N-phenyl-gamma-aminopropyltriethoxysilane, N-butyl-gamma-aminopropyltrimethoxysilane, N-butyl-gamma-aminopropyltriethoxysilane, N-ethyl-3-aminopropyltrimethoxysilane and N-ethyl-3-aminopropyltriethoxysilane;
the mercaptosilane is selected from gamma-mercaptopropyltrimethoxysilane and/or gamma-mercaptopropyltriethoxysilane.
3. The one-part, low modulus polyurethane sealant according to claim 1, wherein said isocyanate b is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate trimer, isophorone diisocyanate trimer and hexamethylene diisocyanate trimer.
4. The one-component low-modulus polyurethane sealant according to claim 1, wherein the molar ratio of the isocyanate b to the silane is 1: 0.8-2.0;
the reaction temperature is 50-70 ℃, and the reaction time is 1-4 h.
5. The one part low modulus polyurethane sealant according to claim 1, wherein said plasticizer a is selected from one or more of the group consisting of alkyl sulfonates, phthalates, cyclohexane dicarboxylates, phosphotriesters and citrate triesters;
the filler is selected from one or more of ground silica, ground calcium carbonate, talcum powder, clay, organic bentonite, hydrogenated castor oil and barium sulfate;
the water absorbent is selected from one or more of alkyl sulfonic acid isocyanate, calcium oxide and molecular sieve;
the catalyst a is selected from tertiary amine catalysts and/or tin catalysts.
6. The one-part low modulus polyurethane sealant according to claim 1, wherein the monoamine compound is selected from one or more of methylamine, ethylamine, n-propylamine, n-butylamine, pentylamine, n-hexylamine, n-octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, aniline, methylaniline, ethylaniline, diphenylamine, dimethylaniline and diethylaniline;
the isocyanate a is selected from toluene diisocyanate, diphenylmethane diisocyanate, 1, 4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, tolidine diisocyanate, 1, 5-naphthalene diisocyanate, triphenylmethane triisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, trans-cyclohexane-1, 4-diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, TDI trimer, IPDI trimer, HDI trimer, polymeric MDI, biuret group-modified MDI, isocyanurate group-modified MDI, urethane group-modified MDI, MDI, One or more of uretdione group-modified MDI, carbodiimide group-modified MDI, and allophanate group-modified MDI;
the plasticizer b is one or more selected from alkyl sulfonate, phthalate, cyclohexane dicarboxylate, phosphate triester and citrate triester.
7. The one-part, low modulus polyurethane sealant according to claim 1, wherein said polyurethane prepolymer is prepared by reacting a polyether polyol and an isocyanate c in the presence of a catalyst b;
the polyether polyol is selected from polyether triol with the molecular weight of 3000-6000 and/or polyether diol with the molecular weight of 1000-4000;
the isocyanate c is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, 1, 4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, tolidine diisocyanate, 1, 5-naphthalene diisocyanate, triphenylmethane triisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, trans cyclohexane-1, 4-diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane and dicyclohexylmethane diisocyanate;
the catalyst b is selected from one or more of dioctyltin dilaurate, dibutyltin dilaurate, dimethyltin dilaurate, stannous octoate, butyltin oxide and octyltin oxide.
8. A method for preparing the one-component low-modulus polyurethane sealant according to any one of claims 1 to 7, comprising the steps of:
and uniformly mixing the polyurethane prepolymer, the plasticizer, the filler, the water absorbent and the thixotropic agent under a vacuum condition, adding the synthetic coupling agent and the catalyst a, and uniformly stirring to obtain the high-thixotropy and fast-curing single-component low-modulus polyurethane sealant.
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| CN114958280A (en) * | 2022-06-30 | 2022-08-30 | 中山市卡施力顿建材有限公司 | Bi-component rock plate adhesive and preparation method and application thereof |
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